Insecticide



Patented Mar. 2, 1943 2,312,301

UNITED STATES PATENT OFFICE w'n Craig, Philadelphia, and William F. Hester, Drexel Hill, Pa., assignors to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application June 28, 1940. Serial No. 342,894

Claims. (Cl. 167-30) This invention relates to insecticidal composlwas washed with aqueous alkali to remove any tions the active principle of which is an allyl or unreacted phenol and with aqueous hydrochloric methallyl ether of a nitrophenol. acid to remove the dimethylaniline and finally These ethers are designated by the general with water. The benzene was then evaporated formula 5 and the residue heated under reduced pressure at 100 0.; 1223 g. of methallyl p-tenbutyl-o- R gggcni?= nitropheriyl ether was thus obtained as an oil.

Example 3 in which X is hydrogen or a methyl group and R my be hydrogen, halogen. or en elkyl erelkylcc. of water, 21 s. of dlmethylaniline and 40 g. of gfgg g g g gg fi 232 2 232 2 2 352 allyl chloride was stirred and heated at refluxing t m at r f i h During mm more than one such substituent and may z gg s g 2%;: gi z iz g i g also contain a. second nitro group. These ethers Arte c 1 th can be prepared by condensing allyl chloride or g 5 gg l sg i g grxg is; fi z gig zg gg ig g gg figg figg i g which was removed and extracted with 200 cc. of

alum petroleum ether (B. P. 60-100" 0.). The solu- Out thls g gg'g zg f g f tion thus obtained was added to the oily layer ploy abou a me 0 8 Y e e Per and this was then extracted four times with 2N- of Sodium hydwxide as this increases the hydrochloric acid to remove the dimethylaniline, lg fi l examples will Illustrate the washezd with water and then extracted four times Wmg with N-sodium hydroxide to remove any unremethod Preparing the elm and methanyl acted phenol. This solution was then washed ethel's 0f the Ophemls- V with water, filtered and the solvent evaporated. Example 1 1x111 tlhls tallay 68 grambst 01in gatertilairigo-nitrophgnyl'sla yeerwasoa wconanas p i ig tg r z or e ka g lg g g fi g 5.1g? of nitrogen, calc. 5.96%, B. P.

v C. mm. phenol), 2.035 kg. of methallyl chloride, 122 g. of A ong t phenols which may be employed in aqueous Solution of g i r 908 place of those in the foregoing examples are: of dlmethylarliline and 1 11 0 was Diamylnltrophenol, caprylnitrophenol, (chloror g g-vgfii fia g igg fig ig 55 8L: ter.butyl)nitrophenol, o-chloro-p-nitrophenol, orose to 97 C. After cooling? the solid material gfffigflfifi f f ifit i fgi'gfififiggfiggg was dissolved in three liters 01 ethylene 'i methaliylnitrophenol, m-nitrophenol, cyclohexyli; rona o e lnltro hen l, r N/1 sodium hydroxide solution followed by 22.5 40 p teiamyl o fi g l f i fi fifigt liters of N/l hydrochloric acid and finally with methYlbuWl)- o l, tetra. 7.5 liters of water. The solvent was then evapomethylbutyl) m rated and the resldue heated at l00 C. and 28 w employed as insecticides these Ethel-s lg ggg udg zl etg gfigglga gg 1 may be aplpliet: in the form of a solution in an o anic so ven as an a ueous-eln i fractional distillation, the fraction boiling at argustmcombmmon wmfan inert g iggffl fig 128-145 C./2 mm. being the desired product. articular method em lo ed will I tabout 80% of the crude produ t g s f i firge extent on the ins ect or class f i nggct be his range. It may also be purine bydisso v g combattei w used a a t 450 s. in 1.1 liters of hot petroleum ether (B. P. $5,, such as red spiders, gg ffifi g g clarifying the 5011mm w Che-r6031 in a suitable organic liquid which has no deletern e- The product separates as a ions arm on the'foliage and this solution is colored solid melting at 38-40 C- emulsified in water with the help of a suitable Example 2 emulsifying agent such as a sulfonated oil which is usually dissolved in the organic liquid prior A mixture or 976 s. of o-nitro-p-ter.bu y1 to emulslfication. A suitable formula for this phenol, 905 g. of methallyl chloride, 450 g. o! 5 type of spray is: sodium hydroxide, 302.5 g. of dimethylaniline and Parts 4 liters of water was heated for six h urs t r Active ingredient 1 0 fluxing temperature. The resulting mixture was Emulslfying agent i'o extracted with benzene. The benzene solution Pine oil "a 2:0

Concentration 1: 1200:

One part of this solution is emulsified in 100 to 400 parts of water depending on the concentration of the active ingredient required for any special case, thus yielding emulsions in which the concentration of the active ingredient ranges from about one part in 400 (1:400) to about one part in 1600 (1:1600). The emulsion thus prepared is sprayed on the infested plants. When employed against aphids on nasturtium the following results were obtained:

Concentration 1 1600:

Per cent kill in 24 hours o-Nitiophenyl methallyl ether 36 p-ter. Butyl-o-nitrophenyl methallyl ether 66 p-ter. Amyl o nltrophenyl methallyl ether 91 p (cam 7,7 Tetramethylbutyl) o nitro phenyl methallyl ether 55 p-ter. Butyl-o-nitrophenyl allyl ether--- 53 In no case was there any injury to the foliage.

Against mealy bugs on coleus the following results were obtained:

Concentration l 1200:

Per cent kill in 24 hours p ter. Butyl o nitrophenyl methallyl ether 59 p ter. Amy] o nitrophenyl methallyl ether p (snap ,7 Tetramethylbutyl) o nitro phenyl methallyl ether 81 No injury to the foliage.

Against red spider on bush beans:

Per cent kill in 24 hours o-Nitrophenyl methallyl ether 32 p-Nitrophenyl methallyl ether 95 p-NitrophenyI-methaIIyI ether 90 p ter. Butyl o nitrophenyl methallyl ether 90 p ter. Amyl nitrophenyl methallyl ether 84 p ter. Amyl o nitrophenyl methallyl ether 9'1 p-(u -Tetramethy1butyl) o nitrophenyl methallyl ether '78 p-ter. Butyl-o-nitrophenyl allyl ether 100 No injury to the foliage.

Against 2-spotted mite on phlox:

Concentration 1:1200:

Per cent hill in 24 hours p (a,a,'y,'y Tetramethylbutyl) o nitro phenyl methallyl ether 81 No inJury to the foliage.

V The nitrophenyl-methallyl ethers can also be spread on inert powders and used in the form of dry dust or suspended in water to combat various insects. The dusts may be prepared by dissolving the ether and a spreading agent in a suitable solvent such as acetone, adding a finely divided solid such as talc, lime, alum sludge, etc. and evaporating the solvent while stirring constantly to insure uniform distribution of the active material. The finished dust may contain from 1 to 10% of the active ingredient. Suitable formulas for such dusts are: I 1

A 2% dust similar to the one shown under A in which the active ingredient was p-nitrophenyl methallyl ether killed 94% of the aphids on nasturtium in 24 hours.

Sprays tOcombat chewing insects can be made by depositing a larger amount of the active in gredient on a powder, adding a wetting agent and dispersing the powder in suilicient water to give the desired concentration of active ingredient. A suitabie'formula ior such a spray is as follows:

Parts by weight Active ingr 1 Magnesium carbonate 2 Emulsifying agent 0.5 Water 96.5

This spray was applied to bush beans and, after standing for 24 hours, bean beetle larvae were applied to the plants. At the end of 48 hours the following results were noted:

Active ingredient D agg i- Pzr cent Per :(nt

o-Nitrophenyl met lyl ether p-ter.Butyl-o-nitrop enyl methallyl other.

The foregoing examples illustrate the use of nitrophenyl methallyl ethers as the sole toxic ingredient of insecticidal preparations. They may, however, also be used in combination with other well known insecticidal principles, such as derris, rotenone, nicotine sulfate, organic thiocyanates, and various inorganic preparations including the arsenic poisons and copper fungicides. Such combinations may be designed to give a plurality of effects or a single improved efiect.

We claim:

1. An insecticidal composition in which the active principle is a methallyl ether of nitro-substituted phenols of the benzene and naphthalene series. i

2. An insecticidal composition in which the active principle is a methallyl ether. of. nitro-substituted alkyl phenols of the benzene and naphthalene series.

3. An insecticidal composition in which the active principle is a'n'itrophenyl methallyl ether.

4. An insecticidal composition in which the active principle is p-ter. butyl-o-nitrophenyl methallyl ether. Y

5. An insecticidal composition in which the active principle is p-(a,, ,-y-tetramethylbutyl)-onitrophenyl methallyl ether.

W E GRAIG. WILLIAM F. HESTER. 

